Process for the simultaneous pro



Patented Sept. 21, 1943 PROCESS FOR THE SIMULTANEOUS PRO. DUCTION OFPETROLEUM SULPHONIC ACID BODIES AND A STABLE LUBRICAT- ING OIL Pharez G.Waldo, Paul M. Goodloe, 2nd, and Henry G. Berger, Woodbury, N. J.,assignors to Socony-Vacuum Oil Company, Incorporated, New York, N. Y., acorporation of New York 'No Drawing. A plication March 8, 1940,

Serial No. 322,970

5 Claims. (01. 196-40) A further object is to provide useful sul-.

phonated solvent tar products.

For many years lubricating oil fractions were acid treated withsulphuric acid to remove undesirable constituents such as unsaturates,etc.-

With the advent of solvent refining, acidtreating of lubricating oilswas greatly reduced, since, as is well known, the solventspreferentially extracted the undesirable constituents leaving thedesirable constituents. Many solvents have been proposed and used in thesolvent refining of, petroleum oils, as for instance, furfural, sulphurdioxide, Chlorex (dichloro-diethyl ether) etc. Also combinations ofsolvents such as acetone and benzol have been used. Still further aprecipitant for undesirable constituents, such as propane, and asolvent, such as cresylic acid, have been used together. Propane hasalso been used alone as an asphalt precipitant, in order to precipitatea substantially oil-free asphaltic product, ,however, this invention isnot concerned with such a product. In the usual solvent refiningprocesses, a rafiinate and an extract or solvent tar are produced. Theraffinate is the refined oil. The extract or solvent tar containsundesirable constituents extracted by at least one solvent therefor.

Heretofore solvent tars have been thought of generally as productscontaining only undesirable constituents insofar as lubricants areconcerned. Accordingly, while portions of solvent tars have been used asfuel oils and for other uses, it is quite surprising to find that astable lubricating oil may be produced from solvent tars.

According to our invention a petroleumsolvent tar which hasbeenextracted from a lubricating oil distillate fraction by solventrefining, is subjected to a relatively heavy acid treatment sufiicienttosulphoriate a portion thereof to yield a sulphonated solvent tarproduct and an unsulphonatable oil, the unsulphonatable oil is thenfurther refined or treated to produce a finished lubricating oil whichis stable to our invention must, of course, be derived from thetreatment of sufiiciently heavy fractions to contain hydrocarbons oflubricating oil range.

As has beenindicated above, there are numerous petroleum solvent tars orextracts produced by the use of numerous solvents and combinationsthereof, e. g'., furfural, liquid sulphur dioxide, Chlorex,benzol-acetone, Duo-Sol (propane and cresylic acid) etc. Moreover, thesesolvent tars are produced from nearly every type of crude, comprising ineach case the less paraffinic portions of the oil treated. In accordancewith our invention any of these solvent tars or extracts from adistillate oil may be used to obtain our stable lubricating oil, and Weparticularly prefer furfural and Chlorex tars.

The solvent tar sulphonic acids produced by our process may be recoveredby any of the well known procedures for recovering sulphonic acidsfrommineral oils in general. After removal of the sulphonic acids orsulphonates there remains a mineral oil which is essentiallyunsulphonatable and which, after blowing bright, to remove ishedlubricant.

occluded water, etc., represents usually from about 10% to of theoriginal solvent tar.

The unsulphonatable oil remaining after the sulphonates are extracted,will require some further treating or refining in order to make a fin-This required treating will depend somewhat on the previous history andnature of the oil. Usually the oil must be blown bright, as noted above,to remove occluded matter and give a bright appearance. Further, de-

waxing may be necessary followed by treatment with clay to give propercolor.

The sulphonation of mineral oil fractions in general is well known aslikewise is the recovery of the sulphonated products. However, in orderto further illustrate the present invention wherein solvent tars aresulphonated, the following specific examples are given:

EXAMPLE I A furfural extract of A. P. I. gravity of 1 2.8 and S. U. V.at 210 F. of 39 which was obtained in 27.5% yield by treating a Mirandodistillate yield of sulphonates was 11.8% by weight of the startingiurfural tar, obtained by extracting the sulphonated oil with dilutealcohol after each oleum dump. The sulphonated material The oil leftafter extracting the sulphonates from the sulphonated Wewoka tar wasblown bright, dewaxed at 20 F. with toluol-acetone and percolatedthrough 10% of its weight of obtained from this furfural tar has thenovel fresh burnt 30-60 fullers earth at 120-130 F. property that thefree sulphonic acids are solu- The following tests were obtained on thisoil; ble in 011, whereas their sodium salts are ina blend (A-W) of 25%of this oil with 75% of a soluble in the same oil. These sodiumsulphonstandard turbine oil (A); and on the standard ates may be used asdetergents. turbine oil (A).

EXAMPLE II A furfural extract of A. P. I. gravity of Wewoka Blendstandard and S. U. V. at 210 F. of 51 was obtained as a 011 kw 34% yieldby treating a Wewoka distillate (Mid- Continent) of A P. I. gravity of28.4 and S. U. 4 5- gravity 5 5 -8 3 at 210 F. of 44 with 250% by volumeof tfulrfurtatl gg fz: "131%: 400 405 380 at 200 t .250 F. This extractwas tre 8 W1 8 g d 22 450 60 lbs. per barrel of 98% sulphuric acid torejg jj" :3 move sludge forming materials. The extract was 8 1683-61-1 32 0 3g 3 then diluted with an equal volume of recovered oil from aformer treatment of the same tar, and g i mmmigmms 1g 1 sulphonated with200 lbs. of Ole m De barrel in German tar. per cent" 0.04 0.03 0.07three equal dumps, separating the sludge between s g gig 3 2&6 37 eachdump. The yield of sulphonates obtained 01m; Lovibon 2 1g 26 onextracting the acid oil, freeing the extract ghdNg-BIIIIIU 00 1 0.110.05 of mineral oil by washing with naphtha, neutl'fl-lizing with stmngcaustic soda" filtermg and 1351110315 A 13 3 mixed Mid-Continent andCoastal 11135111053 evaporating, amounted to 16.1% by weight of thewhich 1103 been acid-treated and then 513 735.

starting furfural tar. v Clear-m The sulphonates from the above WewokaThe particular type oil obtained by our process furfural tar were lightcolored and q ite So e will, of course, depend upon the fraction from ina petroleum oil of A. P. I. gravity of 29.0 to which the solvent tar isobtained. It will be 29.2 and S. U. V. at 100 F. of 100 to 110 seconds.noted that the above Wewoka oil was in the The sulphonates were stableto light, possessed turbine oil range. excellent emulsifying activityand were mm- In a manner similar to that outlined above, corrosive toiron. About 10% by weight, or less, oils have been prepared by ourprocess from with about 10% rosin soap in oil gave a good varioussolvent tars of various crude fractions. soluble cutting oil whichformed stable 1 to 15 In order to further illustrate the invention, theemulsions in soft water and in hard water conproperties of many of theseoils are set forth taining 1000 parts per million hardness. 40 in thefollowing tabular data:

TABLE I Tests on recovered oil Sample No.

1 2 Standard Blend 3 4 1 5 5 7 3 3 10 11 12 Yield .per cent by 3 31.. 3520 37.3 55 17.3 Furiuraltar Wewoka Wewoka Wewoka Ro- 120- R0- MirandoMiranda Oklahoma Stonedessa dessa dessa City wall Fitts 1:1 2:1 2:1 2:12:1 50 50 50 50 50. 50 50 50 50 150 300 200 150 150 100 115 400 250 23.330.3 34.5 30.2 31.3 15.7 15.5 32.5 30.4 0 '70 15 5 5 -20 -25 10 15 330 5305 305 410 405 330 330 Fire 450 435 470 450 455 470 455 375 375 s. U.v.@ F. 152 155 154 132 144 105.2 151.3 143.3 174.0 174.0 134.1 123.4S.U.V.@2l0F 42.5 42.3 43.5 44.2 42.7 40.5 43.7 43.4 40.1 40.1 42.0 41.2v.1 77 35 33 77 05 123 100 110. -103 -103 03.5 38 a; 0.32 1 2.2 0.45 0;0. 0.45 02 0 2 .f N 11 Nil 002 0.0i 0.01 0.05 0.00 Nil 002 Bligh.milllgrams- 13 13 3 13 0 5.0 3 7 17 24 3.4 13 German tar. .per cent wt.0.07 0.03 0.11 0.10 0.00 1.5 0.00 0.03 0.55 0.40 3.5 000 Brown-Boyerlturbine test:

00151, Lovibond 25 10 10 33 5.3 0 0 30 250 370 0 3 N.N 0.07 0.11 0.010.13 0.00 Nil 0.07 0.22 0.31 0.20 0.55 0.05

1 1 1 1 1 1 1 1 1 1 1 1 4 4 4 4 4 4 4 4 4 4 4 4 00 00 00 00 00 00 03 0331 01 00 00 11 7 5.3 11.5 2.4 03 V10 10 55 30 Green 2.3 0.57 0.25 0.110.20 0.00 0.1 0.34 Nil 0.54 0.31 3.0 0.03 10 12 1 12 11 47 20 10 13 21035 2 2 2 2 2 2 2 2 2 2 2 2 3 3 3 3 7 3 3 3 3 3 7 s 135 135 135 133 152133 101 101 135 135 134 135 50 53 45 72 3.4 Green 70 205 240 20 2.4 2.22.3 1.3 0.53 10.5 2.3 5.3 1.3 0. 13.3 1.5 35 42 14 10 30 107 23 45 34 40352 35 The S-V turbine test comprises heating 25 cc. of oil samples at196 periods of time and noting the progressive changes taking place inthe oil in respect to water for increasing acid, color and sludgermatlon.

F. in the presence of copper, iron and It will be noted that in generalall of the above oils produced by our invention are substantially equalto, or even superior to, standard lubricating oils, particularly whenthe proper amount of sulphonation has been used. The oils from thehighly naphthenic Mirando solvent tar, as can be noted, gave unusuallygood turbine oil tests; however, these particular oils do not show upquite so well under other test conditions of oxidation.

It is important that the solvent tars not be undertreated or overtreatedwith the sulphuric acid during sulphonation. For instance in Table Iabove, it may be noted that the oils of columns 6 and 11 are obviouslyovertreated. The proper treatment for producing the best oils willusually be found to be the proper treatment for producing sulphonates.In many cases it may be found preferable to dilute the solvent tar beingtreated with unsulphonated oil rather than out down the amount of acidused. It will be noted that such procedure was followed in the specificExample II and in certain of the runs of Table I.

Since solvent tars vary considerably in the amount and nature ofundesirable constituents contained therein, the amount of acid treatmentmust necessarily vary, however, the optimum conditions of treatment maysoon be arrived at by a few adjustments, particularly since thesulphonation of petroleum fraction is so well known to the petroleumart. In general, the solvent tar usually is first treated with about 94%and/or 98% sulphuric acid to remove sludge forming materials and thenwith about 100 to 400 lbs. per bbl. of oleum to effect the production ofsulphonic acids. As is well known in the field of sulphonic acidproduction, the oleum may be added in either one or several dumps,preferably in a plurality of dumps in the usual operation.

In addition to the stable oils that are produced by our process, it willbe noted that mineral oil sulphonates are produced from the solvent taras a by-product. These sulphonates may be used in the manner in whichany such sulphonates are now used, depending upon whether they are oilor water soluble. For instance, the oil soluble solvent tar sulphonatesmay be used in soluble oils and the water soluble sulphonates may beused as detergents. We have found that, in general, when the solventtars have anvA. P. I. gravity below about 16 they produce water soluble,relatively oil insoluble sulphonates, while if the original solvent tarhas an A. P. I. gravity above about 16 the resultant sulphonates are oilsoluble and relatively water insoluble.

We claim:

1. A process for the simultaneous production of petroleum sulphonic acidbodies and a stable lubricating oil which comprises subjecting solventextract of a distillate lubricating oil stock to a sulphonationtreatment with strong sulphuric acid to obtain a substantial amount ofunsulphonated oil containing petroleum sulphonic acids dissolvedtherein, separating said sulphonic bodies remaining in the unsulphonatedoil from such oil, and thereafter refining the unsulphonated oil so asto produce a stable lubricating oil therefrom.

2. The process of claim 1 wherein the sulphonation treatment of thesolvent extract is carried out in the presence of added unsulphonatedpetroleum oil which has been obtained from the product of a sulphonationtreatment of a similar oil.

3. A process for the simultaneous production of a petroleum sulphonateand a stable lubricating oil which comprises subjecting a furfuralsolvent extract of a distillate lubricating oil stock to a sulphonationtreatment with strong sulphuric acid to obtain a. substantial amount ofunsulphonated oil containing petroleum sulphonic acids dissolvedtherein, recovering said sulphonic acids remaining in the unsulphonatedoil as a sulphonate product, and thereafter refining the unsulphonatedoil so as to produce a stable lubricating oil.

4. The process of claim 1 wherein the solvent extract being sulphonatedhas an A. P. I. gravity below about 16.

5. A process for the simultaneous production of a water soluble,substantially oil insoluble, mahogany petroleum sulphonate and a stablelubricating oil which comprises subjecting a distillate lubricating oilstock furfural solvent extract having an A. P. I. gravity below 16 to asulphonation treatment with strong sulphuric acid to obtain asubstantial amount of unsulphonated oil, containing mahogany sulphonicacids dissolved therein, recovering said sulphonic acids remaining inthe unsulphonated oil as a water soluble, substantially oil insolublesulphonate, and thereafter refining the unsule phonated oil so as toproduce a stable lubricating oil.

PHAREZ. G. WALDO. PAUL M. GOODLOE, 2m. HENRY G; BERGER.

